US20230006219A1 - Supported metal catalyst and electrochemical cell - Google Patents

Supported metal catalyst and electrochemical cell Download PDF

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Publication number
US20230006219A1
US20230006219A1 US17/782,964 US202017782964A US2023006219A1 US 20230006219 A1 US20230006219 A1 US 20230006219A1 US 202017782964 A US202017782964 A US 202017782964A US 2023006219 A1 US2023006219 A1 US 2023006219A1
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Prior art keywords
support
fine particles
metal
metal catalyst
gas
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Inventor
Katsuyoshi Kakinuma
Makoto Uchida
Akihiro Iiyama
Isao Amemiya
Chisato Arata
Sumitaka Watanabe
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Nihon Kagaku Sangyo Co Ltd
University of Yamanashi NUC
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Nihon Kagaku Sangyo Co Ltd
University of Yamanashi NUC
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Assigned to NIHON KAGAKU SANGYO CO., LTD. reassignment NIHON KAGAKU SANGYO CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WATANABE, SUMITAKA, AMEMIYA, ISAO, ARATA, Chisato
Assigned to UNIVERSITY OF YAMANASHI reassignment UNIVERSITY OF YAMANASHI ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IIYAMA, AKIHIRO, KAKINUMA, KATSUYOSHI, UCHIDA, MAKOTO
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/648—Vanadium, niobium or tantalum or polonium
    • B01J23/6486—Tantalum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/067—Inorganic compound e.g. ITO, silica or titania
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a support and metal catalyst and to an electrochemical cell.
  • the support and metal catalyst of the present invention can be used, for example, as a catalyst for electrochemical reaction in an electrochemical cell.
  • the electrochemical cell is intended to mean a cell which performs an electrochemical reaction.
  • a fuel cell which generates electricity by electrochemical reaction using fuel such as hydrogen and methanol
  • a hydrogen purification and pressure booster device which generates purified hydrogen gas with high pressure and high purity from hydrogen-containing gas by an electrochemical reaction
  • a redox flow battery which performs charge and discharge by redox reaction
  • a water electrolysis cell which decompose water into hydrogen and oxygen by an electrochemical reaction
  • Patent Literature 1 discloses a support and metal catalyst in which metal catalyst is supported on a support structured with titanium oxide doped with a different kind of metal.
  • the support and metal catalyst are used as a catalyst layer of an anode of a fuel cell system.
  • Patent Literature 1 WO 2016/203679
  • the present invention has been made by taking these circumstances into consideration.
  • the present invention provides a support and metal catalyst with improved electric conductivity.
  • a support and metal catalyst comprising: a support powder; and metal fine particles supported on the support powder; wherein: the support powder is an aggregate of support fine particles; the support fine particles have a chained portion structured by a plurality of crystallites being fusion bonded to form a chain; the support fine particles are structured with metal oxide; and the metal oxide is doped with a dopant element, and an atomic ratio of titanium with respect to total of titanium and tin is 0.30 to 0.80, is provided.
  • the present inventors have conducted intensive research, and have found that when the atomic ratio of titanium with respect to the total of titanium and tin in the metal oxide constituting the support fine particles is 0.30 to 0.80, electric conductivity becomes particularly high, thereby leading to completion of the invention.
  • FIG. 1 shows a model diagram of a catalyst structure of support and metal catalyst 100 .
  • FIG. 2 shows a view in which support fine particles 150 are taken from FIG. 1 .
  • FIG. 3 shows a condition of branch 160 of the support fine particles 150 of FIG. 1 .
  • FIG. 4 shows a gas diffusion route of FIG. 1 .
  • FIG. 5 shows one example of the distribution of void 110 contained in the support powder.
  • FIG. 6 shows one example of TEM image of the support and metal catalyst 100 .
  • FIG. 7 shows a model diagram of a fuel cell system.
  • FIG. 8 shows a sectional view which is cut through the center of burner 2 of a manufacturing apparatus 1 for manufacturing the support powder.
  • FIG. 9 shows an enlarged view of region X in FIG. 8 .
  • FIG. 10 shows a sectional view taken along the line A-A of FIG. 8 .
  • FIG. 11 shows an enlarged view of region Y in FIG. 10 .
  • FIG. 12 shows a flow of the supporting and reduction step of the metal fine particles 130 .
  • FIG. 13 shows a graph of the measurement results of electric conductivity.
  • the support and metal catalyst 100 comprises a support powder which is an aggregate of support fine particles 150 having a chained portion structured by fusion bonding a plurality of crystallites 120 into a chain, and metal fine particles 130 being supported on the support powder.
  • a three-dimensional void 110 surrounded by the branch 160 and pores existing between a plurality of branches is formed.
  • a plurality of crystallites 120 structuring the support fine particles 150 is fusion bonded to form a chained portion, thereby forming the branch 160 .
  • Gas diffusion route to diffuse and transfer oxygen as the oxidant and/or hydrogen as the fuel to the support and metal catalyst 100 is formed by the three-dimensional arrangement of the support fine particles 150 described above.
  • the support fine particles 150 comprise four pores of a first pore surrounded by points b 1 , b 2 , b 5 , b 4 , and b 1 , where the branches link with each other (may be referred to as branching points, or merely as branch); a second pore surrounded by branching points b 1 , b 2 , b 3 , and b 1 ; a third pore surrounded by branching points b 2 , b 3 , b 6 , b 7 , b 5 , and b 2 ; and a fourth pore surrounded by branching points b 1 , b 3 , b 6 , b 7 , b 5 , b 4 , and b 1 .
  • the void 110 is a three-dimensional space surrounded by the four pore planes.
  • the support fine particles 150 comprise a plurality of pores surrounded by a plurality of branching points in which a plurality of branches link with each other.
  • the three-dimensional spaces (voids) which are surrounded by the plurality of pores are provided sequentially, thereby structuring the support fine particles.
  • the void serves as the gas diffusion route (gas diffusion path) of oxygen, hydrogen and the like.
  • FIG. 4 shows the gas diffusion route in FIG. 1 .
  • FIG. 4 shows one example of the gas diffusion route (gas diffusion path) of void 110 is shown.
  • Flow (gas diffusion route) 170 of oxidant (gas), fuel gas and the like can flow in the desired direction via the void 110 as shown in FIG. 4 . That is, the void 110 serves as the gas diffusion route.
  • the support fine particles 150 can have only one pore (for example, the first pore surrounded by the branching points b 1 , b 2 , b 5 , b 4 , and b 1 ). In such case, a void 110 having a thickness of the crystallite grain of the crystallite 120 is provided.
  • the support fine particles 150 can have one or more branches. In such case, the branches within the support fine particles 150 prohibits cohesion of the support fine particles, thereby providing void 110 between the support fine particles.
  • the “pore” mentioned above can also be mentioned as closed curve (closed loop). Otherwise, it can be said that a void 110 surrounded by a closed plane including the afore-mentioned plurality of branching points (for example, branching points b 1 to b 7 ) is provided.
  • branching points b 1 to b 7 the center of gravity of the crystallite of the metal oxide structuring the support fine particles 150 in which the branches connect with each other can be taken as the branching point, or an arbitrary point in the crystallite can be taken as the branching point.
  • the support fine particles 150 have a branch 160 comprising a chained portion which is structured by fusion bonding a plurality of crystallites 120 into a chain.
  • the branch 160 itself has a nature to allow electrons to flow.
  • the support fine particles 150 have a plurality of branches 160 , and the branches connect with each other at branching points (b 1 to b 7 ), by which a network is structured. Electrically conductive nature can be seen among these. Accordingly, the branches 160 of the support fine particles 150 shown by the dotted line from point PO in FIG. 1 itself structures an electron conduction route (electron conduction path) 140 .
  • the size of the crystallite 120 is preferably 1 to 100 nm, more preferably 5 to 40 nm.
  • the size is, particularly for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 50, or 100 nm, and can be in the range between the two values exemplified herein.
  • the size of the crystallite 120 (crystallite diameter) can be obtained in accordance with a Sheller formula using half-width in the XRD pattern peak.
  • the aggregate of the support fine particles 150 is in the form of a powder. Such aggregate is referred to as “support powder”.
  • the mean particle size of the support fine particles 150 in the support powder is in the range of 0.1 ⁇ m to 4 ⁇ m, preferably in the range of 0.5 ⁇ m to 2 ⁇ m.
  • the mean particle size of the support fine particles 150 can be measured with a laser diffraction/scattering particle size distribution analyzer.
  • the specific surface area of the support powder is preferably 12 m 2 /g or more, and is more preferably 25 m 2 /g or more.
  • the specific surface area is, for example, 12 to 100 m 2 /g, particularly for example, 12, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 m 2 /g, and can be in the range between the two values exemplified herein.
  • the distribution of the void 110 contained in the support powder is shown in FIG. 5 .
  • the distribution of the void 110 can be obtained by measuring the volume of the three-dimensional void of the support powder by using a mercury porosimetry.
  • volume per one void is obtained from the number of voids and the measured volume value, and then a cumulative size distribution is shown as a value of a diameter of a sphere, the sphere being obtained by converting the obtained volume to sphere (sphere equivalent diameter by mercury injection method).
  • void of 11 nm or smaller (primary pore) and void of larger than 11 nm (secondary pore) preferably exist in the support powder. Accordingly, gas diffusion route is secured.
  • the support powder preferably has a void fraction of 50% or higher, more preferably 60% or higher.
  • the void fraction is, for example, 50 to 80%, particularly for example, 50, 55, 60, 65, 70, 75, or 80%, and can be in the range between the two values exemplified herein.
  • the void fraction can be obtained as the ratio of the bulk density of the support powder molded with a uniaxial pressure molding machine (molded body size: 5 mm ⁇ 5 mm ⁇ 30 mm, molding pressure: 2 MPa or less) to the true density of the support powder, mercury press-in method, or FIB-SEM.
  • the support powder preferably has a repose angle of 50 degrees or less, and more preferably a repose angle of 45 degrees or less.
  • the support powder has a similar flowability as flour, and thus handling is simple.
  • the repose angle is, for example, 20 to 50 degrees, particularly for example, 20, 25, 30, 35, 40, 45, or 50, and can be in the range between the two values exemplified herein.
  • the repose angle can be obtained by drop volume method.
  • the support fine particles 150 are structured with metal oxide.
  • the metal oxide is doped with dopant element.
  • the dopant element is an element having a different valence than titanium and tin.
  • As the dopant element at least one is selected among rare earth elements such as yttrium, Group 5 elements such as niobium and tantalum, Group 6 elements such as tungsten, and Group 15 elements such as antimony.
  • Group 5 elements represented by niobium and tantalum, or Group 6 elements represented by tungsten are preferred, and tantalum, niobium, antimony or tungsten are particularly preferred. Tantalum or tungsten are particularly preferred due to their large solid solution capacity.
  • the atom ratio of the dopant element with respect to the entire metal contained in the metal oxide is preferably 0.05 to 0.30. In such case, the electric conductivity of the support and metal catalyst 100 becomes particularly high.
  • the atom ratio is, particularly for example, 0.05, 0.10, 0.15, 0.20, 0.25, or 0.30, and can be in the range between the two values exemplified herein.
  • the metal oxide is preferably a complex oxide of titanium and tin, and the atomic ratio of titanium with respect to the total of titanium and tin is preferably 0.30 to 0.80, more preferably 0.40 to 0.80. In such case, the electric conductivity of the support and metal catalyst 100 becomes high.
  • the atom ratio is, particularly for example, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, or 0.80, and can be in the range between the two values exemplified herein.
  • the metal fine particles 130 are fine particles of metal or metal alloy which can serve as a catalyst.
  • the metal fine particles 130 preferably contain platinum, and the metal fine particles 130 are more preferably platinum.
  • the mean particle size of the plurality of metal fine particles 130 supported on the support powder is 3 to 10 nm.
  • the mean particle size is, particularly for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm, and can be in the range between the two values exemplified herein. When the mean particle size of the metal fine particles 130 is smaller than 3 nm, the metal fine particles would dissolve along with the progress of the electrode reaction.
  • the metal fine particles 130 are, among the particles shown in the transmission image of support and metal catalyst 100 obtained by TEM in FIG. 6 , particles that are dispersed on the surface of the crystallites ( 120 ) having a crystallite size of 1 to 100 nm and having higher contrast than the crystallites.
  • the size of such metal fine particles can be obtained by measuring the diameter of the circumscribed circle of all of the imaged metal fine particles 130 , and calculating their arithmetic mean.
  • the metal fine particles 130 preferably comprise a core and a skin layer covering the core.
  • the core preferably comprises an alloy of a noble metal and a transition metal.
  • the skin layer preferably comprises a noble metal.
  • the noble metal platinum is preferable.
  • the transition metal cobalt (Co) or nickel (Ni) are preferable, and cobalt is especially suitable.
  • titanium is contained in the metal fine particles 130 in a solid solution state.
  • titanium is contained as a solid solution more in the core than the skin layer. Accordingly, when titanium is contained as a solid solution more in the core, activity of the core can be improved.
  • the amount of the metal fine particles 130 being supported is preferably 1 to 50 mass %, more preferably 5 to 25 mass %.
  • the amount being supported is, particularly for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 mass %, and can be in the range between the two values exemplified herein.
  • the electrochemical active surface area of the support and metal catalyst 100 is preferably 20 m 2 /g or more. This surface area is, for example, 20 to 200 m 2 /g, and is particularly for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, or 200 m 2 /g, and can be in the range between the two values exemplified herein.
  • the electrochemical active surface area can be obtained by the rotating ring disk electrode method or cyclic voltammetry (sweep rate of 0.1 V/sec. or less) of membrane electrode assembly.
  • FIG. 7 A model diagram of the fuel cell according to the present invention is shown in FIG. 7 .
  • the fuel cell 200 is structured by aligning the catalyst layer 220 A and the gas diffusion layer 210 A on the anode 201 side, and the catalyst layer 220 K and the gas diffusion layer 210 K on the cathode 202 side, facing each other with the electrolyte membrane 230 in between. That is, the gas diffusion layer 210 A on the anode side, the catalyst layer 220 A on the anode side, the electrolyte membrane 230 , the catalyst layer 220 K on the cathode side, and the gas diffusion layer 210 K on the cathode side are aligned in this order.
  • power is output to the load 203 .
  • At least one of the catalyst layer 220 A on the anode side and the catalyst layer 220 K on the cathode side is formed with the support and metal catalyst 100 . More preferably, the catalyst layer 220 A on the anode side is formed with the support and metal catalyst 100 .
  • the electric resistance of the support and metal catalyst 100 is larger under oxygen atmosphere than under hydrogen atmosphere. Therefore, when the support and metal catalyst 100 is used for the catalyst layer 220 A on the anode side, occurrence of oxygen reduction reaction at the catalyst layer 220 A on the anode side is suppressed when the fuel cell is started or shutdown. Therefore, corrosion reaction of the catalyst layer 220 K on the cathode side is suppressed even when the support thereof is carbon. Accordingly, degradation of power generation performance of the fuel cell is suppressed.
  • catalysts disclosed in Patent Literature 1 catalysts structured by supporting metal fine particles on support of ceramics (for example, tin oxide, titanium oxide) other than the metal oxide of the present invention, and catalysts structured by supporting metal fine particles on carbon support, can be mentioned.
  • the manufacturing apparatus 1 which can be used for the manufacture of the support powder is explained.
  • the manufacturing apparatus 1 comprises a burner 2 , a raw material supplying unit 3 , a reaction cylinder 4 , a collector 5 , and a gas reservoir 6 .
  • the raw material supplying unit 3 comprises an outer cylinder 13 , and a raw material distribution cylinder 23 .
  • the burner 2 is a cylinder, and the raw material supplying unit 3 is arranged in the burner 2 .
  • Burner gas 2 a is distributed between the burner 2 and the outer cylinder 13 .
  • the burner gas 2 a is used to form a flame 7 at the tip of the burner 2 by ignition.
  • a high temperature region having a temperature of 1000° C. or higher is formed by the flame 7 .
  • the burner gas 2 a preferably contains a combustible gas such as propane, methane, acetylene, hydrogen, or nitrous oxide.
  • a gas mixture of oxygen and propane can be used as the burner gas 2 a .
  • the temperature of the high temperature region is 1000 to 2000° C. for example, and is particularly for example, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, or 2000° C., and can be in the range between the two values exemplified herein.
  • a raw material solution 23 a for generating the support powder is distributed in the raw material distribution cylinder 23 .
  • the one containing a titanium compound and tin compound is used.
  • the titanium compound and tin compound fatty acid titanium and fatty acid tin can be mentioned for example.
  • the number of carbon atoms in the fatty acid is, for example, 2 to 20, preferably 4 to 15, and further preferably 6 to 12.
  • As the fatty acid octylic acid is preferable.
  • the raw material solution 23 a can contain metal compound for doping the support fine particles 150 .
  • metal compound fatty acid metal (Nb, Ta, W and the like) salt can be mentioned for example.
  • the number of carbon atoms in the fatty acid is, for example, 2 to 20, preferably 4 to 15, and further preferably 6 to 12.
  • niobium octylate, tantalum octylate, antimony octylate, and tungsten octylate are preferable.
  • the titanium compound and the tin compound are preferably dissolved or dispersed in a non-aqueous solvent.
  • a non-aqueous solvent organic solvent represented by terpen can be mentioned. If moisture is contained in the raw material solution 23 a , fatty acid titanium and fatty acid tin can undergo hydrolysis and degrade.
  • Mist gas 13 a used for converting the raw material solution 23 a into a mist is distributed in between the outer cylinder 13 and the raw material distribution cylinder 23 .
  • the mist gas 13 a and the raw material solution 23 a are jetted together from the tip of the raw material supplying unit 3 , the raw material solution 23 a is converted into a mist.
  • the mist 23 b of the raw material solution 23 a is sprayed into the flame 7 , and the titanium compound and the tin compound in the raw material solution 23 a undergoes a thermal decomposition reaction in the flame 7 . Accordingly, support powder which is an aggregate of support fine particles 150 having a chained portion structured by fusion bonding the crystallite 120 into a chain is generated.
  • the mist gas 13 a is oxygen in one example.
  • the reaction cylinder 4 is provided between the collector 5 and the gas reservoir 6 .
  • the flame 7 is formed in the reaction cylinder 4 .
  • the collector 5 is provided with a filter 5 a and a gas discharging portion 5 b .
  • a negative pressure is applied to the gas discharging portion 5 b . Accordingly, a flow which flows towards the gas discharging portion 5 b is generated in the collector 5 and the reaction cylinder 4 .
  • the gas reservoir 6 has a cylinder shape, and comprises a cold gas introducing portion 6 a and a slit 6 b .
  • a cold gas 6 g is introduced from the cold gas introducing portion 6 a into the gas reservoir 6 .
  • the cold gas introducing portion 6 a is directed in a direction along the tangential line of the inner peripheral wall 6 c of the gas reservoir 6 . Therefore, the cold gas 6 g introduced through the cold gas introducing portion 6 a into the gas reservoir 6 revolves along the inner peripheral wall 6 c .
  • a burner insertion hole 6 d is provided at the center of the gas reservoir 6 . The burner 2 is inserted through the burner insertion hole 6 d .
  • the slit 6 b is provided in the vicinity of the burner insertion hole 6 d so as to surround the burner insertion hole 6 d . Accordingly, when the burner 2 is inserted through the burner insertion hole 6 d , the slit 6 b is provided so as to surround the burner 2 .
  • the cold gas 6 g in the gas reservoir 6 is driven by the negative pressure applied to the gas discharging portion 5 b , and is discharged from the slit 6 b towards the reaction cylinder 4 .
  • the cold gas 6 g can be any gas so long as it can cool the metal oxide generated, and is preferably an inert gas, for example, air.
  • the flow speed of the cold gas 6 g is preferably two times or more of the flow speed of the burner gas 2 a .
  • the upper limit of the flow speed of the cold gas 6 g is not particularly limited, and is 1000 times the flow speed of the burner gas 2 a for example.
  • the ratio of flow speed of cold gas 6 g /flow speed of burner gas 2 a is 2 to 1000 for example, and the ratio is particularly for example, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 100, 200, 500, or 1000, and can be in the range between the two values exemplified herein.
  • a negative pressure is applied to the gas discharging portion 5 b to allow the cold gas 6 g to flow, however, a positive pressure can be applied to the gas introducing portion 6 a to allow the cold gas 6 g to flow.
  • the support fine particles 150 After the support fine particles 150 come out of the flame 7 , the support fine particles 150 would be immediately cooled by the cold gas 6 g , thereby allowing to maintain the structure having the chained portion. The support fine particles 150 after cooling would be trapped by the filter 5 a and collected. The trapped support fine particles 150 can be subjected to heat treatment at 400 to 1000° C. to adjust the crystallite diameter.
  • the support powder which is an aggregate of the support fine particles 150 can be manufactured by using the manufacturing apparatus 1 .
  • a high-temperature region of 1000° C. or higher is formed at the tip of the burner 2 by the flame 7 , and the titanium compound and the tin compound are allowed to undergo a thermal decomposition reaction in this high-temperature region while supplying the cold gas 6 g through the slit 6 b to the surroundings of the high-temperature region.
  • the high-temperature region can be formed by plasma instead of the flame 7 .
  • the method for manufacturing support and metal catalyst 100 comprises a supporting step and a reduction step.
  • the metal fine particles 130 are supported on the support powder.
  • Such supporting can be performed by a reverse micelle method, a colloidal method, an impregnation method and the like.
  • the supporting step of the colloidal method comprises an adsorbing step and a heat treatment step.
  • the metal colloidal particles are adsorbed onto the support powder. More particularly, the metal colloidal particles synthesized by the colloidal method is dispersed in an aqueous solution to prepare a dispersion, and then the metal colloidal particles are added and mixed in the dispersion. Accordingly, the colloidal particles are adsorbed onto the surface of the support powder. The support powder having the colloidal particles adsorbed thereon is then filtered and dried, thereby being separated from the dispersion medium.
  • the metal of the metal colloidal particles include platinum.
  • heat treatment is performed at 100 to 400° C. after the adsorbing step to convert the metal colloidal particles into metal fine particles 130 .
  • the temperature of the heat treatment is, particularly for example, 100, 150, 200, 250, 300, 350, or 400° C., and can be in the range between the two values exemplified herein.
  • the heat treatment duration time is, for example, 0.1 to 20 hours, preferably 0.5 to 5 hours.
  • the heat treatment duration time is, particularly for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 hours, and can be in the range between the two values exemplified herein.
  • Heat treatment can be carried out under an inert gas atmosphere such as nitrogen, or under an inert gas atmosphere containing 1 to 4% of hydrogen.
  • reduction treatment of the metal fine particles 130 is carried out after the heat treatment step.
  • the reduction treatment can be carried out by performing a heat treatment under a reductive atmosphere containing a reductive gas such as hydrogen.
  • the temperature of this heat treatment is, for example, 70 to 300° C., preferably 100 to 200° C.
  • This temperature is, particularly for example, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 250, or 300° C., and can be in the range between the two values exemplified herein.
  • the heat treatment duration time is, for example, 0.01 to 20 hours, preferably 0.1 to 5 hours.
  • the heat treatment duration time is, particularly for example, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 hours, and can be in the range between the two values exemplified herein.
  • the concentration thereof is, for example, 0.1 to 100 volume %, preferably 0.2 to 10 volume %, and more preferably 0.5 to 3 volume %.
  • Thins concentration is, particularly for example, 0.1, 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 10, or 100 volume %, and can be in the range between the two values exemplified herein.
  • the metal fine particles 130 after the heat treatment in the supporting step can be in an oxidized condition. In such case, the metal fine particles 130 may not show catalyst activity.
  • the catalyst activity can be increased by reducing the metal fine particles 130 .
  • the support and metal catalyst was manufactured in accordance with the method described below, and various evaluations were performed.
  • support powder was manufactured.
  • gas prepared by blending 5 L/min of oxygen and 1 L/min of propane gas was used. This gas was ignited to form a flame (chemical flame) 7 of 1600° C. or higher at the tip of the burner 2 .
  • the raw material solution 23 a was prepared by blending titanium octylate, tin octylate, and tantalum octylate by a molar ratio of 0.40:0.60:0.10, and then the blend was further combined with mineral spirit terpen and dissolved. Oxygen was used as the mist gas 13 a.
  • the raw material supplying unit 3 comprises a double tube structure (overall length of 322.3 mm).
  • Oxygen is supplied from the outer cylinder 13 , and the raw material solution 23 a is supplied to the raw material distribution cylinder 23 .
  • a fluid nozzle and an air nozzle are provided, and the raw material solution 23 a was converted into the mist 23 b at this position.
  • the amount of the support powder collected was 10 g or more when the operation was carried out for 60 minutes.
  • metal fine particles 130 were supported onto the support powder.
  • Step S 1 of FIG. 12 First, 0.57 mL of chloroplatinic acid hexahydrate aqueous solution was dissolved in 38 ml of super pure water, followed by addition of 1.76 g of sodium carbonate, and then the mixture was agitated (Step S 1 of FIG. 12 ).
  • the solution was diluted with 150 ml of water, and pH of the solution was adjusted to 5 with NaOH. Thereafter, 25 ml of hydrogen peroxide was added, and the pH was again adjusted to 5 with NaOH (Step S 2 of FIG. 12 ).
  • a dispersion prepared by dispersing 0.50 g of support powder in 15 mL of super pure water was added (Step S 3 of FIG. 12 ), and the mixture was agitated for 3 hours at 90° C. (Step S 4 of FIG. 12 ).
  • the mixture was cooled to room temperature, and was then filtered.
  • the residue was washed with super pure water and alcohol, and was then dried overnight at 80° C.
  • the residue was then subjected to heat treatment at 400° C. for 2 hours under nitrogen atmosphere to support the metal fine particles 130 onto the support powder.
  • heat treatment at 150° C. for 2 hours under 1% hydrogen atmosphere was performed to reduce the metal fine particles 130 (Step S 5 of FIG. 12 ). Accordingly, support and metal catalyst 100 as metal fine particles 130 supported on support powder was obtained.
  • Support and metal catalyst 100 were manufactured in a similar manner as Example 1, except for altering the molar ratio of titanium octylate, tin octylate, and tantalum octylate as shown in Table 1.
  • the support and metal catalyst 100 according to the Examples had higher electric conductivity compared with the support and metal catalyst 100 according to the Comparative Examples.
  • the atom ratio of Ti/((Ti+Sn) had greater influence on the electric conductivity in the support and metal catalyst 100 , compared with the support powder.
  • the method for measuring the electric conductivity is as follows.
  • Target sample 8 samples
  • the 8 samples were each filled into 8 sample holders (3 mm diameter, 5 mm depth) in the measurement tool, respectively.
  • the measurement tool filled with the target samples was set in a pressure device, and the target samples were compressed with a force of 1.1 kN.
  • the electrode provided with the compression tool of the pressure device the resistance of the target sample during compression was measured by the DC two-terminal method, and the length of the target sample was also measured at the same time.
  • the relation between the length of the target sample (x axis) and resistance (y axis) during compression was obtained, and extrapolation towards the y axis was performed to obtain the y intercept.
  • the specific resistance of the target sample was obtained from the value of the y intercept, length and cross-sectional area of the compressed powder.
  • the electric conductivity was calculated as the inverse of the specific resistance.

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